1,2,4-Triazole-containing compounds and their use as pesticides

ABSTRACT

Plant fungicidal compounds of formula: ##STR1## WHEREIN R 1  is hydrogen, or nitro, R 3  is alkyl, furyl, thienyl or phenyl, R 4  is hydrogen, halogen, nitro, phenyl, alkoxy or alkyl, n is 1, 2 or 3, and Z is C ═ O or a derivative thereof; and their salts.

This invention relates to heterocyclic compounds which are imidazole or1,2,4-triazole compounds, to a process for preparing them, tocompositions containing them and to a method of combating fungal pestsusing them.

The compounds have the general formula (I): ##STR2## WHEREIN Y is ═N--or ═C(R)--, each of R, R₁ and R₂, which may be the same or different, ishydrogen, halogen, nitro or alkyl (e.g. methyl, ethyl, propyl or butyl);R₃ is hydrogen or furyl, thienyl or hydrocarbyl optionally substitutedwith halogen, acyloxy, cyano, hydroxy, nitro, alkoxy or unsubstituted orhalo-substituted alkyl; R₄ is hydrogen, halogen, nitro, phenyl, alkoxyor unsubstituted or halo-substituted alkyl; n is an integer of 1 to 5;and Z is C ═ O or a derivative thereof (e.g. an imine, oxime, ketal,hydrazone or semicarbazone), or salts of said compounds.

The compounds form geometrical isomers. The invention includes withinits scope such isomers each of which can be isolated from mixturesthereof by methods known in the art.

The term "hydrocarbyl" as used herein refers to monovalent organicradicals composed of hydrogen and carbon. The hydrocarbyl may besaturated or unsaturated, straight or branched chain or single ring;examples are alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl andalkaryl.

The hydrocarbyl is preferably C₁₋₇, especially C₁₋₆, hydrocarbyl, e.g.methyl, ethyl, propyl (n- or iso-propyl), butyl (n-, iso- or t-butyl),amyl, hexyl, heptyl, allyl, propynyl, phenyl, benzyl and substitutedphenyl and benzyl. The alkoxy is suitably C₁₋₇ alkoxy, e.g. methoxy,ethoxy, propoxy or butoxy.

The halogen can be fluorine, chlorine, bromine or iodine. A suitablyacyloxy group is acetoxy.

As indicated above, R₃ can be substituted phenyl. Specific examples ofsuch groups are 2-chloro- or fluorophenyl, 3-fluorophenyl, 4-fluoro-,chloro-, nitro-, n-butoxy-, methoxy-, cyano-, hydroxy- oracetoxy-phenyl, 2,4-, 3,4- or 2,6-dichlorophenyl, 2,4-dimethoxyphenyl orbiphenyl.

Another suitable R₃ group is trichloromethyl.

When R₃ is thienyl or furyl, it is preferably 2-thienyl, 2-furyl or5-chloro-2-thienyl.

When n is 1, R₄ is preferably fluorine, chlorine or phenyl. When n is 2,the two R₄ groups are preferably halogen, e.g. two chlorine atoms in 2-and 4-positions. A suitable halo-substituted alkyl is trifluoro- ortrichloromethyl.

The salts can be salts with inorganic or organic acids, e.g.hydrochloric, nitric, sulphuric, acetic or oxalic acid.

Examples of suitable triazole and imidazole compounds are given in,respectively, Tables I and II, wherein Z is C ═ O.

                  TABLE I                                                         ______________________________________                                                                             Melting (Or                              Compound                             Boiling) Point                           No      R.sub.1                                                                             R.sub.2                                                                             R.sub.3     R.sub.4                                                                            ° C                               ______________________________________                                        1       H     H     n-C.sub.3 H.sub.7                                                                         4-Cl (165° /0.5                                                             mm Hg)                                   2       H     H     C.sub.6 H.sub.5                                                                           4-Cl 115-117°                          3       H     H     4-Cl--C.sub.6 H.sub.4                                                                     4-Cl 186-188°                          4       H     H     C.sub.6 H.sub.5                                                                           H    125-127°                          5       H     H     4-NO.sub.2 --C.sub.6 H.sub.4                                                              4-Cl 161-163°                          6       H     H     4-MeO--C.sub.6 H.sub.4                                                                    4-Cl 79-82°                            7       H     H     4-Cl--C.sub.6 H.sub.4                                                                     H    115-116°                          8       H     H     4-CN--C.sub.6 H.sub.4                                                                     H    128-132°                          9       H     H     2-thienyl   4-Cl 113-114°                          10      H     H     2-furyl     H    112-114°                          11      H     H     2,4-di-Cl--C.sub.6 H.sub.3                                                                4-Cl  98-101°                          12      H     H     4-F-C.sub.6 H.sub.4                                                                       4-Cl 167-169°                          13      H     H     2,4-di-MeO--C.sub.6 H.sub.3                                                               4-Cl 127-129°                          ______________________________________                                    

                  TABLE II                                                        ______________________________________                                        Compound                                                                              R, R.sub.1                                                            No      and R.sub.2                                                                           R.sub.3     R.sub.4  M.P. (° C)                        ______________________________________                                        28      H       4-Cl--C.sub.6 H.sub.4                                                                     4-Cl     120-122°                          29      H       4-Cl--C.sub.6 H.sub.4                                                                     2,4-di-Cl                                                                              46-48°                            30      H       2,6-di-Cl--C.sub.6 H.sub.3                                                                4-F      115-117°                          31      H       2,6-di-Cl--C.sub.6 H.sub.3                                                                4-F      95-97°                            32      H       4-Cl--C.sub.6 H.sub.4                                                                     4-F      143-145°                          33      H       4-NO.sub.2 --C.sub.6 H.sub.4                                                              4-F      55-58°                            34      H       2,4-di-Cl--C.sub.6 H.sub.3                                                                4-Cl     130-132°                          35      H       2,4-di-Cl--C.sub.6 H.sub.3                                                                H        120-122°                          36      H       4-NO.sub.2 --C.sub.6 H.sub.4                                                              H        154-156°                          37      H       4-Cl--C.sub.6 H.sub.4                                                                     H        85-87°                            38      H       2-Cl--C.sub.6 H.sub.4                                                                     4-Cl     147-149°                          39      H       4-NO.sub.2 --C.sub.6 H.sub.4                                                              4-Cl     112-114°                          40      H       2-Cl--C.sub.6 H.sub.4                                                                     H        109-110°                          41      H       4-NO.sub.2 --C.sub.6 H.sub.4                                                              4-F      143-144°                          42      H       4-NO.sub.2 -- C.sub.6 H.sub.4                                                             H        158-160°                          43      H       2,6-di-Cl--C.sub.6 H.sub.3                                                                H        117-119°                          44      H       2-F-C.sub.6 H.sub.4                                                                       H        130-132°                          45      H       2,6-di-Cl--C.sub.6 H.sub.3                                                                H        168-170°                          46      H       2-F--C.sub.6 H.sub.4                                                                      4-Cl     129-131°                          47      H       C.sub.6 H.sub.5                                                                           H        108-110°                          48      H       3-F--C.sub.6 H.sub.4                                                                      H        130-132°                          49      H       4-F--C.sub.6 H.sub.4                                                                      H        85-86°                            50      H       C.sub.6 H.sub.5                                                                           4-Cl     148-150°                          51      H       C.sub.6 H.sub.5                                                                           4-F      133-135°                          52      H       3-F--C.sub.6 H.sub.4                                                                      4-Cl     131-132°                          53      H       2-Cl--C.sub.6 H.sub.4                                                                     4-F      105-107°                          54      H       4-F--C.sub.6 H.sub.4                                                                      4-F      120-121°                          55      H       2,6-di-Cl--C.sub.6 H.sub.3                                                                4-Cl     115-116°                          56      H       2-Cl--C.sub.6 H.sub.4                                                                     2,4-di-Cl                                                                              102-104°                          57      H       C.sub.6 H.sub.5                                                                           2,4-di-Cl                                                                              76-78°                            58      H       3,4-di-Cl--C.sub.6 H.sub.3                                                                2,4-di-Cl                                                                              129-131°                          59      H       2,6-di-Cl--C.sub.6 H.sub.3                                                                2,4-di-Cl                                                                              126-128°                          60      H       4-F--C.sub.6 H.sub.4                                                                      2,4-di-Cl                                                                              86-88°                            61      H       5-chloro-2- H                                                                 thienyl                                                       62      H       n-Pr        4-Cl                                              63      H       2,4-di-Cl--C.sub.6 H.sub.3                                                                4-Ph                                              ______________________________________                                    

It is believed that Compounds 1 to 22, 24 to 40, 43, 44 and 46 to 63have the configuration (A), and that Compounds 23, 41, 42 and 45 aregeometric isomers of Compounds 12, 33, 36 and 43, respectively, and itis believed that they have the configuration (B). ##STR3##

The compounds of general formula (I) may be made by reacting a compoundof general (II): ##STR4## wherein Z, Y, R₁, R₂, R₄ and n are as definedabove, or a salt thereof, with an optionally substituted aldehyde, usingmethods set out in literature.

The reaction is suitably performed in the presence of a convenient basesuch as piperidine or pyridine in a high boiling hydrocarbon solvente.g. toluene. Suitably a few drops of glacial acetic acid are present inthe reaction mixture as a catalyst.

This process is generally performed by refluxing the reactants togetherin a solvent and, after allowing reaction to occur, isolating theproduct by removal of the solvent in vacuo. The product is thencrystallised from a convenient solvent. In some cases both geometricisomers are formed in the reaction and these can be convenientlyseparated by chromatographic techniques. For example, the mixture ofisomers can generally be chromatographed on silica as the stationaryphase using a mixture of ethyl acetate/petroleum ether as the mobileeluent.

The acetophenone starting material of general formula (II) can be madeby reacting an imidazole or triazole with the appropriate α-haloketone(e.g. an α-chloro or bromoketone), using any of the methods set out inthe literature. Usually the α-haloketone, in a convenient solvent(preferably acetonitrile or a hydroxylated solvent), is added to theimidazole or triazole in the same solvent at low temperatures. Theproduct can be isolated by removal of the solvent and extracting theresidue into an organic solvent with washing. Removal of the solventgives the required compound which can be crystallised from a convenientsolvent.

Alternatively, the compounds of general formula (I) can be made bydehydrogenating in known manner a compound of general formula (III):##STR5## wherein n, Y, Z and R₁ to R₄ are as defined above, or a saltthereof. The dehydrogenation can be achieved for example by reactionwith bromine in acetic acid followed by dehydrobromination, or directlyby reaction with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ).

The compounds wherein Z is a derivative of C ═ O may be made from therespective carbonyl compound using any of the standard techniques setout in the literature.

The compounds are active against a wide range of fungal diseases,particularly against the following:

Puccinia recondita and other rusts on wheat and rusts on other hosts

Plasmopara viticola on vines

Erysiphe graminis (powdery mildew) on barley and wheat and other powderymildews on various hosts such as Sphaerotheca fuliginea on cucumbers,Podosphaera leucotricha on apples and Uncinula necator on vines

Botrytis cinerea (grey mould) on tomatoes, strawberries, vines, andother hosts

Piricularia oryzae on rice

Colletotrichum lindemuthianum

Phytophthora infestans (late blight) on potato and tomato

Some of the compounds have also shown a broad range of activitiesagainst fungi in vitro.

Further some of the compounds are active in the form of seed dressingsagainst Fusarium spp., Septoria spp., Tilletia spp. and Pyrenophora spp.on cereals.

They also have certain plant growth regulating, herbicidal,anti-bacterial, algicidal and anti-viral activities.

The compounds may be used as such for anti-fungal purposes but are moreconveniently formulated into compositions.

The invention therefore also provides a fungicidal compositioncomprising, as an active ingredient, an imidazole or triazole compoundor salt thereof as defined above, and a carrier for the activeingredient.

The invention also provides a method for combating fungal diseases in aplant, which method comprises treating the plant, seed of the plant orthe locus surrounding the plant or seed with an imidazole or triazolecompound or salt thereof as hereinbefore defined.

The compounds can be used to combat plant pests and treat plants orseeds in a number of ways, for example they can be applied, formulatedor unformulated, directly to the foliage of a plant which is infected orlikely to become infected, or they can be applied also to bushes andtrees, to seeds or to other medium in which plants, bushes or trees aregrowing or are to be planted, or they can be sprayed on, dusted on orapplied as a cream or paste formulation. Application can be to any partof the plant, bush or tree, for example to the foliage, stems, branchesor roots, or to soil surrounding the roots.

The term "treating" as used herein refers to all these modes ofapplication and the term "plant" includes seedlings, bushes and trees.Furthermore, the method of the invention includes preventative,protectant, prophylactic and eradicant treatment.

The compounds are preferably used for agricultural and horticulturalpurposes in the form of a composition. The type of composition used inany instance will depend upon the particular purpose envisaged.

The compositions may be in the form of dusting powders or granulescomprising the active ingredient and a solid diluent or carrier, forexample, kaolin, bentonite, kieselguhr, dolomite, calcium carbonate,talc, powdered magnesia, Fuller's earth, gypsum, Hewitt's earth,diatomaceous earth and China clay. Compositions for dressing seed, forexample, may comprise an agent (for example a mineral oil) for assistingthe adhesion of the composition to the seed.

The compositions may also be in the form of dispersible powders orgrains comprising a wetting agent to facilitate the dispersion inliquids of the powder or grains which may contain also fillers andsuspending agents.

The aqueous dispersions or emulsions may be prepared by dissolving theactive ingredient(s) in an organic solvent optionally containingwetting, dispersing or emulsifying agent(s) and then adding the mixtureto water which may also contain wetting, dispersing or emulsifyingagent(s). Suitable solvents are ethylene dichloride, isopropyl alcohol,propylene glycol, diacetone alcohol, toluene, kerosene,methylnaphthalene, the xylenes and trichloroethylene.

The compositions to be used as sprays may also be in the form ofaerosols wherein the formulation is held in a container under pressurein the presence of a propellant, e.g. fluorotrichloromethane ordichlorodifluoromethane.

By including suitable additives, for example additives for improving thedistribution, adhesive power and resistance to rain on treated surfaces,the different compositions can be better adapted for various utilities.

The compounds can be used as mixtures with fertilisers (e.g. nitrogen --or phosphorus -- containing fertilisers). Compositions comprising onlygranules of fertiliser incorporating, for example coated with, thetriazole compound, are preferred. The invention therefore also providesa fertiliser composition comprising the compound.

The compositions may also be in the form of liquid preparations for useas dips or sprays which are generally aqueous dispersions or emulsionscontaining the active ingredient in the presence of one or more wettingagent(s), dispersing agent(s), emulsifying agent(s) or suspendingagent(s). These agents can be cationic, anionic or non-anionic agents.

Suitable cationic agents are quaternary ammonium compounds for example,cetyltrimethylammonium bromide. Suitable anionic agents are soaps, saltsof aliphatic monoesters of sulphuric acid (for example sodium laurylsulphate), and salts of sulphonated aromatic compounds (for examplesodium dodecylbenzenesulphonate, sodium, calcium or ammoniumlignosulphonate, butylnaphthalene sulphonate, and a mixture of sodiumdiisopropyl- and triisopropyl-naphthalene sulphonates). Suitablenon-ionic agents are the condensation products of ethylene oxide withfatty alcohols such as oleyl alcohol or cetyl alcohol, or with alkylphenols such as octylphenol, nonylphenol and octylcresol. Othernon-ionic agents are the partial esters derived from long chain fattyacids and hexitol anhydrides, the condensation products of the saidpartial esters with ethylene oxide, and the lecithins. Suitablesuspending agents are hydrophilic colloids (for examplepolyvinylpyrrolidone and sodium carboxymethylcellulose), and thevegetable gums (for example gum acacia and gum tragacanth).

The compositions for use as aqueous dispersions or emulsions aregenerally supplied in the form of a concentrate containing a highproportion of the active ingredient(s), the concentrate to be dilutedwith water before use. These concentrates often should be able towithstand storage for prolonged periods and after such storage becapable of dilution with water in order to form aqueous preparationswhich remain homogeneous for a sufficient time to enable them to beapplied by conventional spray equipment. The concentrates mayconveniently contain 10-85%, generally 25-60%, by weight of the activeingredient(s). When diluted to form aqueous preparations, suchpreparations may contain varying amounts of the active ingredient(s)depending upon the intended purpose, but an aqueous preparationcontaining 0.0005% or 0.01% to 10% by weight of active ingredient(s) maybe used.

The compositions of this invention can comprise also other compound(s)having biological activity (e.g. growth stimulating substances such asthe gibberellins), as well as stabilising agent(s), for example epoxides(e.g. epichlorhydrin).

The following Examples illustrate the invention; the temperatures aregiven in degrees Centrigrade (° C).

EXAMPLE 1 1-(1,2,4-Triazol-1-yl)-p-chlorophenacylstyrene

(Compound 2)

Stage I. To α-bromo-p-chloroacetophenone (4.64 g) in acetonitrile (50ml) was added 1,2,4-triazole (1.4 g) followed by triethylamine (2 g).The mixture was stirred at room temperature for two hours and refluxedfor one hour. The solvent was removed under reduced pressure and to theresidue water was added. The yellow solid which precipitated wasfiltered, washed with water and dried. Crystallisation fromethanol-petroleum ether (60°-80°) gaveα-1,2,4-triazol-1-yl-p-chloroacetophenone as cream coloured plates, m.p.148°-150°.

Stage II. α-1,2,4-Triazol-1-yl-p-chloroacetophenone (3.35 g),benzaldehyde (1.59 g) and piperidine (6 drops) in toluene (30 ml) wererefluxed in a azeotropic set up until no more water separated; this tookabout eight hours. The toluene was removed in vacuo and the residue wastaken up in methylene chloride. The organic layer was washed with water,dried (MgSO₄) and the solvent was removed. The residual oil solidifiedon cooling. Crystallisation from ethanol-petroleum ether (60°-80°) gavethe title compound as a yellow crystalline solid, m.p. 115°-117°.

Compound 2 can also be made by the following procedure.α-Benzyl-α-triazol-1-yl-p-chloroacetophenone (1.6 g) in acetic acid (15ml) was treated with bromine (0.8 g) and the mixture was refluxed forsix hours. The thin layer chromatography over silica gel showed that twocomponents were present in the reaction mixture and there was no changeafter further refluxing. Acetic acid was then evaporated off in vacuo.The residue was treated with water and was extracted with methylenechloride. The organic layer was washed with water, sodium bicarbonatesolution and water and was then dried (Na₂ SO₄). The solvent wasremoved, and the residual oil was chromatographed over silica gel(60-120 mesh) eluting with petroleum ether (60°-80°) ethyl acetate (1:1)to give, in low yield, the title compound as a pale yellow solid, m.p.115°-117°.

EXAMPLE 2 1-(1,2,4-Triazol-1-yl)-1-p-chlorophenacyl-p-fluorostyrene

(Compounds 12 and 23)

α-1,2,4-Triazol-1-yl-p-chloroacetophenone (25 g), p-fluorobenzaldehyde(14.25 g), piperidine (10 drops) and acetic acid (20 drops) in toluene(200 ml) were refluxed in an azeotropic set up until no more waterseparated out; this took about two hours. Removal of toluene gave ayellow solid which was crystallised from ethyl acetate/petroleum ether(60°-80°). One of the geometrical isomers of1-(1,2,4-triazol-1-yl)-1-p-chlorophenyl-p-fluorostyrene was obtained asa yellow crystalline solid, m.p. 167°-169°. The other isomer wasisolated from the filtrate by preparative thin layer chromatography onsilica gel (Merck silica gel F-254) using ethyl acetate/petroleum ether(60°-80°) (1:1) as the eluent. Crystallisation from ethylacetate/petroleum ether (60°-80°) gave this isomer, m.p. 114°-115°.

EXAMPLE 3 1-Imidazol-1-yl-1-phenacyl-o-fluorostyrene

(Compound 44)

Stage I. Phenacyl bromide (0.05 mol) and imidazole (0.02 mol) werestirred in methanol (50 ml) at 0° for 3 hours. The methanol was removedin vacuo and the residue taken up in methylene chloride (300 ml), washedwith water (3 × 100 ml), and dried (anhydrous sodium sulphate). Removalof the solvent left a solid residue which on recrystallisation fromethyl acetate gave 2-(imidazol-1-yl)-acetophenone (60% ) as light brownneedles, m.p. 112°-113°.

Stage II. 2-(Imidazol-1-yl)-acetophenone (0.03 mol),2-fluorobenzaldehyde (0.03 mol), piperidine (2 drops), and glacialacetic acid (4 drops), were refluxed in toluene (25 mls) for 10 hours.The solvent was then removed in vacuo and the resultant brown solidwashed with ethyl acetate/petroleum ether. Recrystallisation from ethylacetate gave 1-imidazol-1-yl-1-phenacyl-o-fluorostyrene as pale yellowcrystals.

EXAMPLE 4 1-Imidazol-1-yl-1-phenacyl-p-nitrostyrene

(Compounds 36 and 42)

2-(Imidazol-1-yl)-acetophenone (0.03 mol), 4-nitro benzaldehyde (0.03mol), piperidine (2 drops), and glacial acetic acid (4 drops), wererefluxed in toluene (50 ml) for 10 hours. The solvent was then removedin vacuo and the resultant brown solid purified by column chromatographyon silica eluting with ethyl acetate/petroleum ether (7:3) to giveCompound 42 as a pale yellow crystalline solid, m.p. 158°-160° (ethylacetate/petroleum ether), and Compound 36 as a pale yellow crystallinesolid, m.p. 154°-156° (ethyl acetate/petroleum ether).

EXAMPLE 5

The imidazole and triazole compounds were tested against a variety offoliar fungal diseases of plants. The technique employed was as follows.

The plants were grown in John Innes Potting Compost (No. 1, or Seed, asappropriate) in 4 cm diameter mini-pots. A layer of fine sand was placedat the bottom of the pot to facilitate uptake of test compound by theroots. Vermiculite was used to cover the seed in the soil tests.

The test compounds were formulated either by bead-milling with aqueousDispersol T or as a solution in acetone/ethanol which was diluted to therequired concentration immediately before use. For the foliage diseases,100 ppm a.i. suspensions were sprayed on to the foliage and applied tothe roots of the same plant via the soil. (Sprays were applied tomaximum retention, and root drenches to a final concentration equivalentto approximately 40 ppm a.i./dry soil). Tween 20, to give a finalconcentration of 0.1%, was added when the sprays were applied to thecereals.

For most of the tests, the test compound was applied to the soil andfoliage one or two days before the plant was inoculated with thediseases. An exception was the test on Erysiphe graminis, in which theplants were inoculated 24 hours before treatment. After inoculation, theplants were put into an appropriate environment to allow infection totake place and then incubated until the disease was ready forassessment. The period between inoculation and assessment varied from 4to 14 days according to the disease and environment.

The disease control was recorded by the following grading:

4 = No disease

3 = 0-5%

2 = 6-25%

1 = 26-60%

0 = >60%

The results are shown in Table III.

                                      TABLE III                                   __________________________________________________________________________    DISEASE CONTROL                                                                                               Botrytis                                            Puccinia                                                                            Phytophthora                                                                         Plasmopara                                                                          Piricularia                                                                          cinerea                                                                            Erysiphe                                 Compound                                                                            recondita                                                                           infestans                                                                            viticola                                                                            oryzae in   graminis                                 No    in wheat                                                                            in tomato                                                                            in vines                                                                            in rice                                                                              tomatoes                                                                           in barley                                __________________________________________________________________________    1     3     2      3     0      0    4                                        2     3     2-3    3     3      2-4  4                                        3     1-2   0      2-3   0      0    4                                        4     3     0-1    --    0      --   4                                        5     3     0      --    0-1    3    4                                        6     1-2   1-2    --    0      2-3  4                                        7     3     0      --    0      3    4                                        8     3     3      --    0      3    4                                        9     2     2      0     0      2    4                                        10    1     0      0     0      0    4                                        11    4     2      2     0      0    4                                        12    3     0      1     0      0    3                                        13    1     0      1     --     1    4                                        14    1     3      2     --     3    4                                        15    1     0      1     --     2    4                                        16    4     0      3     0      0    0                                        17    3     0      3     0      3    4                                        18    3     0      0     --     0    0                                        19    1     0      3     --     0    0                                        20    3     0      2     0      3    4                                        21    4     --     3     3      3    4                                        22    1     0      0     0      0    2                                        23    4     2      3     1      4    4                                        24    0     3      3     --     2    3                                        25    0     3      0     --     0    4                                        26    3     3      2     4      3    3                                        27    3     0      1     0      3    2                                        28    3     0      3     0      1    3                                        29    3     0      4     0      0    4                                        30    3     0      0     --     1    1                                        31    3     0      3     --     0    --                                       32    3     0      2     0      3    4                                        33    3     0      0     2      1    3                                        34    3     2      1     0      2    3                                        35    3     1      3     0      4    4                                        36    3     3      2     1      3    4                                        37    3     3      3     0      3    3                                        38    0     0      0     0      4    3                                        39    3     3      3     1      4    3                                        40    3     2      3     0      4    3                                        41    3     0      1     2      3    4                                        42    3     1      2     0      2    4                                        43    0     --     --    1      3    2                                        44    3     --     --    0      1    3                                        45    1     0      0     0      0    2                                        46    3     --     --    0      1    3                                        47    3     --     --    0      3    3                                        48    3     --     --    0      3    3                                        49    4     0      0     0      4    3                                        50    3     0      0     0      1    2                                        51    3     0      0     0      2    3                                        52    3     2      1     1      3    3                                        53    3     0      0     0      3    3                                        54    4     0      0            3    4                                        55          0      0     3      3    3                                        56    3     2      0     0      4    4                                        57    3     2      1     0      3    4                                        58    1     2      0     0      1    4                                        59    2     3      0     0      2    4                                        60    3     1      2     0      0    3                                        61                                                                            62                                                                            63                                                                            __________________________________________________________________________

We claim:
 1. A compound of formula: ##STR6## wherein R₁ is hydrogen, ornitro; R₃ is alkyl or R₃ is furyl, thienyl or phenyl optionallysubstituted with halogen, acyloxy, cyano, hydroxy, nitro, alkoxy orunsubstituted or halo-substituted alkyl; R₄ is hydrogen, halogen, nitro,phenyl, alkoxy or unsubstituted or halo-substituted alkyl; n is 1, 2 or3; and Z is C = O, or a fungicidal salt of such a compound.
 2. Acompound as claimed in claim 1 wherein R₃ is propyl, phenyl,fluorophenyl, chlorophenyl, nitrophenyl, methoxyphenyl, butoxyphenyl,cyanophenyl, hydroxyphenyl, acetoxyphenyl, dichlorophenyl,dimethoxyphenyl, biphenyl, 2-thienyl or 2-furyl.
 3. A compound asclaimed in claim 2 wherein R₄ is hydrogen, fluorine, chlorine or phenyl.4. A fungicidal composition comprising, as active ingredient, afungicidally effective amount of a compound or salt as claimed in claim1, and a carrier for the active ingredient.
 5. A fungicidal compositioncomprising, as active ingredient, a fungicidally effective amount of acompound or salt as claimed in claim 2, and a carrier for the activeingredient.
 6. A fungicidal composition comprising, as activeingredient, a fungicidally effective amount of a compound or salt asclaimed in claim 3, and a carrier for the active ingredient.
 7. A methodof combating fungal diseases in a plant, the method consistingessentially of the step of applying to the plant, to seed of the plantor to the locus of the plant or seed, a fungicidally effective amount ofa compound or salt as claimed in claim
 1. 8. A method of combatingfungal diseases in a plant, the method consisting essentially of thestep of applying to the plant, to seed of the plant or to the locus ofthe plant or seed, a fungicidally effective amount of a compound or saltas claimed in claim
 2. 9. A method combating fungal diseases in a plant,the method consisting essentially of the step of applying to the plant,to seed of the plant or to the locus of the plant or seed, afungicidally effective amount of a compound or salt according to claim3.
 10. A compound as claimed in claim 3 wherein R₁ is hydrogen.
 11. Acompound as claimed in claim 3 wherein n is 1.